Interface polarizable

A typical example of an ideal polarizable interface is the mercury-solution interface [1,2]. From an experimental point of view it is characterized by its electrocapillary curve describing the variation of the interfacial tension 7 with the potential drop across the interface, 0. Using the thermodynamic relation due to Lippmann, we get the charge of the wall a (-a is the charge on the solution side) from the derivative of the electrocapillary curve ... 

W. R. Fawcett. Molecular models for the solvent structure at polarizable interfaces. Israeli J Chem 75 3-16, 1979. 

Thermodynamically, all metal/solution interfaces are nonpolarizable, i.e., they can exchange electrical charges freely across the phase boundary. It is the extreme slowness of these exchanges that turns a nonpolarizable into a polarizable interface. Therefore polarizable interfaces are a limiting case of nonpolarizable interfaces.2... 

A nonpolarizable interface behaves as a capacitor C and a resistor R in parallel a polarizable interface responds as a pure capacitor. The higher the resistance R, the closer the behavior of the former to the latter. For R —> °o, a nonpolarizable interface becomes polarizable. The condition / — < corresponds to Am —> 0. This condition is met when the amount of M+ in the null solution is negligibly small. 

The situation that no charge transfer across the interface occurs is named the ideal polarized or blocked interface. Such interfaces do not permit, due to thermodynamic or kinetic reasons, either electron or ion transfer. They possess Galvani potentials fixed by the electrolyte and charge. Of course, the ideal polarizable interface is practically a limiting case of the interfaces with charge transfer, because any interface is always permeable to ions to some extent. Therefore, only an approximation of the ideal polarizable interface can be realized experimentally (Section III.D). 

This chapter will include equilibria at non-polarizable interfaces for a metal or semiconductor phase-electrolyte system (a galvanic cell in the broadest sense) and for two electrolytes (the solid electrolyte-electrolyte solution interface, or that between two immiscible electrolyte solutions). 

When we discussed the double-layer properties of metal electrodes in contact with an electrolyte solution, we introduced the notion of an ideally polarizable interface, which is marked by the absence of charge-... 

Ideal polarizable interfaces are critical for the interpretation of electrochemical kinetic data. Ideality has been approached for certain metal electrode-solution interfaces, such as mercury-water, allowing for the collection of data that can be subjected to rigorous theoretical analysis. 

A polarizable Interface is represented by a (polarizable) electrode where a potential difference across the double layer is applied externally, i.e., by applying between the electrode and a reference electrode using a potentiostat. At a reversible interface the change in electrostatic potential across the double layer results from a chemical interaction of solutes (potential determining species) with the solid. The characteristics of the two types of double layers are very similar and they differ primarily in the manner in which the potential difference across the interface is established. 

Under these circumstances [12, 13], the ITIES behaves as an ideally polarizable interface, i.e. within a certain range of electrical potential values between water and the organic phase, attains the value applied from an external source. 

Erdey-Gruz, 1048, 1306 1474 Erschler, 1133, 1134, 1425 Ethylene oxidation, anodic, 1052 1258 Exchange current density, 1049, 1066 correction of, 1069 definition, 1053 electrocatalysis and, 1278 impedance and, 1136 interfacial reaction, 1047 and partly polarizable interface, 1056 Excited states, lifetime, 1478 Exothermic reaction, 1041 Ex situ techniques, 785, 788, 1146... 

Mercaptohexadecanol, adsorption, 979 Mercury in electrode kinetics, 1093, 1195 Mercury solution interface, ideal polarizable interface, 848 Metal capacity, 888 determination. 890 -water interactions, 896, 897... 

The Extreme Cases of Ideally Nonpolarizable and Polarizable Interfaces... 

Are nonpolarizable and polarizable interfaces fictions, or can one find them in the laboratory The fact is that such interfaces can indeed be fabricated and have been used in double-layer studies. Of course, no interface is ideally nonpolarizable or ideally polarizable, i.e., nonpolarizable interfaces do change their potential to some extent and polarizable interfaces do resist such changes to some extent. The distinction is one of degree rather than kind. 

Fig. 6.33. (a) The equivalent circuit for an electrified interface is a capacitor and resistor connected in parallel, (b) In the equivalent circuit for an ideally polarizable interface, the resistance tends to infinity, and fora nonpolarizable interface, the resistance tends to zero. 

Consider mercury as the liquid metal under study. One of the advantages of this metal is that the mercuiy/solution interface approaches closest to the ideal polarizable interface (see Section 6.3.3) over a range of 2 V. What this means is that this interface responds exactly to all the changes in the potential difference of an external source when it is coupled to a nonpolarizable interface, and there are no complications of charges leaking through the double layer (charge-transfer reactions). 

One electrochemical system that can be used to measure the surface tension of the mercuiy/solution interface is shown in Fig. 6.50. The essential parts are (1) a mercuiy/solution polarizable interface, (2) a nonpolarizable interface, (3) an external source of variable potential difference V, and (4) an arrangement to measure the surface tension of the mercuiy in contact with the solution.39... 

What are the capabilities of this system Since the system consists of a polarizable interface coupled to a nonpolarizable interface, changes in the potential of the external source are almost equal to the changes of potential only at the polarizable interface, i.e., the changes in zl< ) across the mercuiy/solution interface are almost equal to changes in potential difference Vacross the terminals of the source. Hence, the system can be used to produce predetermined zl< ) changes at the mercuiy/solution interface (Section 6.3.11). Further, measurement of the surface tension of the mercuiy/solution interface is possible, and since this has been stated /Section 6.4.5) to be related to the surface excess, it becomes possible to measure this quantity for a given species in the interphase. In short, the system permits what are called electrocapillary measurements, i.e., the measurement of the surface tension of the... 

This is the fundamental equation for the thermodynamic treatment of polarizable interfaces. It is a relation among interfacial tension y, surface excess 1 -, applied potential V, charge density qM, and solution composition. It shows that interfacial tension varies with the applied potential and with the solution composition. This is in fact the relation that was desired. Its implications will now be analyzed. 

Now consider a polarizable interface that consists of a metal electrode in contact with a solution of a l l-valent electrolyte (i.e., Z+ = 1 and z = -1). It will be remembered that in order to apply electrocapillaiy thermodynamics to a polarizable interface Mj/S, the interface has to be assembled in a cell along with a nonpolarizable interface. Suppose that the nonpolarizable interface is one at which negative ions interchange charge with the metal surface, i.e., Zj = — 1. Hence, Eq. (6.99) for the polarizable interface becomes... 

The thermodynamic equations applicable to a polarizable interface, which can be studied by means of a capillary electrometer, can now be summarized. The general equation is... 

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